The validity of electrostatic predictions of the shapes of van der Waals dimers

Alistair P.L. Rendell, George B. Bacskay, Noel S. Hush

Research output: Contribution to journalArticle

92 Citations (Scopus)

Abstract

The interaction energies of the van der Waals dimers H2O-H2O, Cl2-HF, ClF-HF and N2O-HF have been calculated for a range of geometries using ab initio SCF techniques. The SCF binding energies have been decomposed into electrostatic, exchange, polarisation and charge-transfer contributions and the intermolecular angles optimised with respect to various combinations of the above components. The effects of exchange, polarisation and charge transfer on the shape of a given dimer are found approximately to cancel, so that in each case a purely electrostatic model is capable of predicting intermolecular angles that agree well with those of a full SCF treatment, as well as with experiment. These findings are consistent with the proposals and earlier calculations of Buckingham and Fowler.

Original languageEnglish
Pages (from-to)400-408
Number of pages9
JournalChemical Physics Letters
Volume117
Issue number5
DOIs
Publication statusPublished - 28 Jun 1985
Externally publishedYes

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